Composition of matter and method of making same



Patented Mar. 27, 1945 fcoMPosITIoN 0E MATTER AND METHOD I OF MAKING SAME Melvin De Groote, University City, and Bernhard T Keiser, -Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, DeL,

, a corporation of Delaware No Drawing. Original applicati n June 23, 1943, Serial No. 492,182. Divided and this application April 7 944, Serial No. 530,044 r 1 1 g This invention relatesto anew chemical product or compound, our present application being a division of our pending application Serial No. 492,182, filed June 23, 1943.

One object of our invention is to provide a new material or composition of matter, that is particularly adapted for use as a demulsifier in'the resolution of crude oil emulsions.

Another object of our invention is to provide a novel method for producing said new material or composition of matter.

Briefly described, our new chemical product or compound consists of the sulfonic acid or sulfonic acid salt or ester of a hydroxy or alkoxy diaryl alkyl methane, in which at least one of the aryl groups contains at least one hydroxy radical, or at least, one nuclear substituted alkoxy radical, the alkyl radical of said alkoxy group having not over ten carbon atoms, and in which there is at least one nuclearly-linked fatty acid radical derived from an unsaturated fatty acid having at least 11 and not over 22 carbon atoms.

Considered in a broad generic sense, the type of aryl sulfonic acid just described, may be referred to as a Twitchell agent, or sulfa-fatty aromatic acid, or sometimes as a sulfo-aromatic fatty acid. Prior reference to the ester formconcerns the carboxyl radical and not the sulfonic acid radical, as is apparent in light of subsequent descrip--' tion. One of the common procedures employed to manufacture sulfo-aromatic fatty acids is to employ a method in which the selected aromatic material and the selected unsaturated fatty acid such as oleic acid, is subjected to a sulfonationcondensation reaction. Such reaction involves the simultaneous introduction of the fatty acid radical into the aromatic nucleus, along with the simultaneous introduction of one or more sulfonic acid radicals. Thus, it is our'preferred procedure to manufacture the herein contemplated com pounds in the manner thus indicated. In light of this preference, it appears most convenient to describe suitable aromatic reactants which may be employed as raw materials.

In numerous instances, and in fact, .it is preferred, to use the type of aromatic reactants in which there are present two phenylol groups, and additionally, two alkyl groups directly attached to the methane nucleus, as, for example, diphenylol dimethyl methane. Such latter reactant may be prepared in the following manner: Phenol is reacted with acetone (or diethyl ketone or methyl ethyl ketone), as described in U. S. Patent No. 1,225,748, of 'WallaceA. Beatty, to give the compound diphenylol dimethyl methane on; canon or the corresponding diethyl or methyl ethyl compound.- Alkyl radicals'attached to methane carbon atom may be replaced by alkylene radicals. Furthermore, the non-aryl methanecarbon atom substituents may be alicyclic or alkylaryl. The lastmentioned raw material represents the type of phenyl-ketone condensation product-known generically in the art as bis-phenols, and are readily available and comparatively inexpensive. As to the manufacture of bis-phenols, reference is made to U. S. Patent No. 2,182,308, dated December 5, 1939, to' Britton 'and'Bryner. Bis-phenols have the general formula: I j lac--11 .HOR

wherein R is an aryl group and the free bonds are linked with alkyl groups or an alkylene radical.

They are commonly prepared by reacting a phen01, e, g., phenol, o-cresol, etc., with a ketone such as acetone, methylethyl ketone, dibenzyl ketone, cyclohexanone, etc.-, in the presence of a concentrated 'strongmineral acid such as sulfuric or hydrochloric "acid" 'Any' ketone, e. g., acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, cyclohexanone, may be employed inthe reaction, and also a-va'riety of phenols can be used, for instance, phenol, o -creso1, o-chlorphenol, etc., are suitable. The aryl radical or radicals, may or may not contain anu'clearsubstituted alkyl radi- Similar reactants are derivable from a variety of other carbonyl-containing compounds, including l retonea'i'n' which the carbonyl oxygen is activated by; the presence of a halogen as a substituentfor'a hydrogen atom; alphachlorina'ted aldehydes,tetc. In theart relatingto this-type of compound they are sometimes described as sub Another suitable type of raw material is exemp-Oumyl phenol (a,a,-Dimetl yl-p-benzyt phenol) Having obtained a diaryl substituted methane-4 of the type previously described and which may contain a nuclear-linked alkyl radical having "not more than 10' carbon atoms, one need onlysubject such reactant to sulfonation, in the presence of a suitable unsaturated fatty acid, inorder --toobtain a material of the kind herein contemplated foruse as such, or after neutralization, or esterification of the carboxyl radical. For instance, if one obtains a propylated or butylated or amylated bis-phenol A, or the equivalent; in which the propyl, butyl, or an'iyl group is directlyattached to the aromatic nucleus; such compound need only be subjected to sulfonationjfollowed by the usual steps for elimination oftheexcess sulfonating agent, such as sulfuric acid, oleum, etc., in order to obtain a raw matriahwhich can be readily converted into asulfo-aromatic fatty compound.- As pointed out subsequently; sulfonation and introduction of the fattyacid-radical are preferably accomplished'in a single-step.

If, however-, one employs a raw material-in which there is no-nuclear substituted alkyl radical, or if it is desirable tointroduce an additional nuclear substituted alkylradical :or radicals; in order to havean alkylated or polyalkylated are matic raw. material, then itis preferable to em ploy a'proceduremfnthe kind commonly used in conversionof naphthalene :to an alkylated naph thalene sulfonic acid. (For zexamplegsee Ur S;

Patent No. 2,309,935, datedFebruary 2, 1943, to

Claytor.) Briefly stated, the process consists in converting the aromatic material, for instance, bis-phenol A in the present instance, into a sulfonic acid. The. sulfonic-aeid-so obtained maybe apolysulfonic acid, for instanceya di-,- .tri-, or tetra-sulfonic acid, but it is preferably a monosulfonic acid. Generallyspeaking, .there is no advantage-in introducing more than one sulfonic acid radical. Furthermore, it is immaterial whether one obtains oneisomeric' sulfonic acid, or another isomeric-sulfonic acid orsamixture. However, as suggestedpreviously, and as pointed out subsequently, alkylation, sulfonation, and introductionof the .fattyacid radical can be accomplished in a single step.

, The alcohol employedgsuch as a methyl,=ethyl, propyl, butyl, amyl, hexyL or decyl alcohol, etc., is converted into the acid sulfate, such as propyl hydrogen sulfate. The aryl sulfonic acid andthe alkyl hydrogen sulfate, are combinedfin proportions so that 1,2, 3,"or even'4, alkyl groups are introduced into the aromatic residue. This consulfuric-acid to -p'roduce the alkyl hydrogen sulfates; Of course, in addition to introducing such alkyl groups of the kind described into the arcmatic nucleus or nuclei, one could also introduce an alkylresidue-from some other alcohol, as, for

examp1e, an a1kylated group derived from cycloheXyl, benzyl, ormethyl alcohol. Such methyl group might be present in the event that the pri mary-raw' material employed happened to be a suitably selected cresol.

It'is immaterial as to the particular alcohol employed,.or the particular isomeric form of the alcohol employed, although generally. speaking, it 'is most desirable to use the one lower or lowest in cost. It is immaterial whether one uses normal propyl alcohol, or isopropyl alcohol. It is immaterial whether one uses a normal butyl alcoholjor isobutyl alcohol. It is' immaterial whether densation reaction is generally carried .out in the alcohol be a primaryalcohol, or a secondary alcohol, or a tertiaryalc'ohol, or the like. This is true whether the alcohol 'is used in preparation of an intermediate, or in a single step involving the final material.

Previous reference'has been made to the fact that an alkyl groupcontaining not more than 10 carbonatoms, can'be present in the aryl reactant. There is, of course, a definite limit to the selection offalk'ylated phenols as raw materials for condensation with a ketone or an aldehyde, in the manufacture of bis ph'enols' or the like. Basically','the reason relates to the activation of a nuclearhydrogen atom by. the hydroXyl-group, so that condensation with elimination of the carbonyl oxygen atom will'take place. As has been previouslypointed out,-.bis-phenols may be obtained from ortho-substituted phenols. Thus, one might use orthobutyl phenol, orthoamyl phenol, etc; The products so obtained serve asraw materials-for the manufacture of the sulfo-aromatic fattyicompoundsl One may, of course, prepare a bis-phenol to be used as a rawin'aterial from unsubstituted phenols, so as to obtaina'reactant of the kind exemplified by bis-phenol "A. Such product contains no nuclear-substituted 'alkyl radicals-containing less than 10' carbon atoms. If, however, one subjects such reactant to some conventional reaction so" as to introduce .an alkyl radical, it mayhappen, and frequently. does happen,-that the alkyl'radical enters at the phenolic hydroxyl hydrogen atom position, rather than at the nuclear position. Reference is-made to-rea-ctions such as the Friedel & Crafts reaction, or any manher of a number of similar reactions-, -in. which the alkylating agent is an alkyl halide containing less than 10 carbon atomsrsuch as propyl chloride, butyl chloride, octyl chloride, decyl chloride, etc. The condensation agent or catalyst maybe exemplified by 2 aluminum chloride, boron trifluoride, zinc chloride, sulfuric-acid, orother equally well'known reagents. Inthe briefest aspossible Joiner (only one nuclear hydrogen atom shown) If one employs such alkylation reaction; on in. troduces either an alkyl group, or an alkoxy group. In light of the fact thatsuch reactions are well known, it is not believed that a further, description is necessary. Havingobtained such suitable reactant by any of the procedures previously described, it is obvious that suchreactant can then be subjected to a sulfonation process or procedure in thejsame manner as employed to sulfonate naphthalene, amyl naphthalene, butylated'phenol, or the like. suchlsulfonation step may be carried on with a minimum of sul-v furic acid, or sulfonating agent, if .conduct'e'ci in the presence of an inert solvent whichielimillates the water formed as a result of" sulfdnationl 'f( see Journal of Industrial'& Engineering Chemistry, volume 35, No. 3, page326 (1943) Again, attention is directed to the fact that the introduction of the fatty acid radical may'take 'placea-tthis same tage I LI... 1

In any event, as a result-of the procedures previously described, one obtains a sulfonic acid suitable for use as a material and containing, at the most, some excess sulfonatingagent', and

possibly, unchanged reactants. In the actual manufacture of alkylated aryl s lfonic; acids,

such as those herein contemplated, the sulfonation step is followed by a, washing process which removes the excess'of'sulfuric acid -onother sulfonation, sulfation, or condensation agentsemployed. Where a condensation-agent;-such-as aluminum chloride or thelike'has been-employed, it is customary'to remove -it, of-w course,

- prior'to the sulfonation step. -'I'he sulfonation mass, briefly stated, is diluted with. sufficient water so that the sulfonicv acid-resulting. from sulfonation is insoluble in the'more-diluteacid. The diluted mass is allowed to stand in aquiescent state until separation takes ;place.. 1- The diluted lower acid also is withdrawn and 'discarded. I .l

Previous reference has been made to the fact that the compounds herein contemplated :are sulfo-aromatic fatty acids or saltsor estersthere'. of, and although they may be manufactured in various ways, one particularly feasible procedure is to employ the method used for the production of Twitchell agents. Broadly speaking; :s'uch method, contemplates reacting an aromatic material and a fatty acid in presence Or -the sulfo'nating and condensing agent. In lightor-iwhatflappears in the previousparagraphs, it is evident that one might introduce both they fatty acid-radical and an alkyl radical, if desired, in. the same reaction, along with the introduction of a sulfonic acid radical. In other words, onemight. adopt ,a procedure in which an aromatic material such as bis-phenolA, an alcohol suches prqpylalcoe hol', if desired, and a fatty acid, such'aso1e c,acid,

A;sulfo aromatio-fatty acid, orits salt orcarboxylic,,ester, may be prepared from sulfo-aro- .matic acid vand an unsaturated fatty acid. In other words, one might react naphthalene sulfonic acid,.o r phenol sulfonic acid with oleic acid, in thepresence of a condensing vagent, suchas strong sulfuric acid. However, there is no reason,

ordinarily, why the two reactions, to wit, s ul fonation, and condensation, should not be carried out simultaneously. If desired, alkylation can also be carried out at the same time. Thus, instead of sulfonating the specific aromatic. reactants previously described and subsequently mixing them with oleicacid, under appropriate conditions, it is more feasible to mix the unsulfonated aromatic reactant, such as bis-phenol A with oleic acidor the like, and subject the entire mass to a sulfonation-condensation reaction. Such procedure is most desirable, for a number of' obvious reasons, and thus, will be illustrated b'y subsequent, examples. Alkylation, such as propyl'ation, can also take place, in the same operation- In view of the prior complete description,.and the well known nature of the'reactants and reaction, this is perfectly obvious to the skilled chemist.

As previously suggested, one class of reactants employed in the production of the herein described sulfoaromatic fatty. acids are higher unsaturatedfatty acids, asexemplified by oleicacid. These unsaturated fatty acids vary in the number of carbon atoms present, from 11 to 22. For instance, unsaturated acids having 11 carbon atomsmay be obtained by pyrolysis of castor oil or ricinoleic acid. Similar acids having as many as 20 to 22 carbon acids are obtainable/from jojoba bean oil, or from other naturally-occurring waxes. Better known examples are oleic acid, erucic acid, and the like. Some of the fatty acids may contain more than 1 ethylene linkage, as, for example, linoleic acid or linolenic acid. Furthermore, one may employ a naturally-occurring mixture of fatty. acids, rather than a single specific acid. .Our preference is to employ the mono-ethylenic acids. i

In any event, the acidic mass resulting from a selected sulfonation-condensationreaction, or its equivalent, asemployed in the manufacture of the herein described sulfo-aromatic fatty acid, is handled in the same manner previously noted in connection with a reaction wherein an alkyl radical or the like is introduced into an aromatic nucleus. In other words, the acidic mass is diluted, permittedto separate, and the acidic mass is esterifled or neutralized. It may be neutralizedin any convenient manner, with a suitable base, such as caustic soda, caustic potash, ammonium hydroxide, or the like. Certain amines, such as benzylamine, amylamlne, cyclohexylamine, octadecylamine, etc., may be employed. The final product, if .it represents a pasty, or solid, or semi-solidmass, is rendered useful for industrial use by the addition of a solvent, such as water, or an alcohol, a. coal tar solvent, a peuelellm hydroc rb n o v r y he se .of

tion is also accelerated'bythe presence *ofal'arge amount of sulfonic acid; Other alcohols, such as soda; caustic'potash, ammonium hydrate, triethanolamine, oxyethylated triethanolamine,

fderived by treating triethanolamine with ethylalicyclicalcohols, aralkyl 'alcohols, includingbenzylalcohol, ethyl-benzyl' alcohol, cyclohexyl a'loohol ethylcyclohexyl alcohol, etc. may beused.

In light of what has been said in the' previous paragraph, inregard to esterification, it is obvious that-if one desires a compound or a mix ture in which the carboxylic radical isesterifled to a greater or lesser degre with an alcoholsuch as propy-l alcohol, butyl alcohol; or one of" the other alcohols previously described, itis possible t'oconduct three or four reactions simultaneously.

The ultimate product must involve at least sulionati'on and the introduction of a fatty acid" radical. The ultimate product may also involve the introduction of an alkyl'radical in the arcmatic nucleus. I-fe'sterification is also involved, and many of the most desirable compounds are obtained at least by the partial esterification of the carboxyl radical, then, in that event, all four reactions of the kind described, to wit:

(a) Sulfonation;

(b) Alkylation;

(0) Nuclear introduction ofa fattyacid radical;

and

(d) Esterification of "the fatty acid carb'oxy'l, may

lene oxide, oxyethylated tris(hydroxymethyl) amifnomethane derived by treating tris(hydroxymethyl) aminomethane with ethylene oxide. These bases enhance water solubility.

Example 2 The same procedure is followed as in Example 1, preceding, except that para-cumyl-phenol is used as a reactant instead of bis-phenol A.

' Example 3 J The same procedure is followed as in Examnle precedin except that phenyl-pheny-lolmethyl methaneoi theloll'owing composition:

is--used=to replace bis-phenol A.

' Ex mp 4 The same procedure is used as in Example. 1, preceding, except that a butylated bis-phenol A, obfialnedby reactingortho-monobutyl phenol with acetone-yin the manner described in the aforementioned. Brittomand Bryner patent, is employediinst'ead-oiibis-phenol A.

take place in the singleoperation procedure.

All of this is obvious, in View of what hasbeen said previously, but will lie-elaborated on by subsequent examples.

Example 1' 1 pound mole of di-phenylo'l .dimethyl methane (bis-phenol A) is mixed with 1 pound mole of oleic acid hydrogen-hydrogen. sulfate, prepared by reacting 1 pound mole of .oleic acid: with 11 to 2 pound moles of-x-sulfuric monohyd-rate and immediately employing the mixture "thus" ohtain'ed. 1 to 2 pound moles :of sulfuric acid 96% or weak oleum are added- The mass is stirred constantly at atemperature which precludes the formation of any significant amount of, sulfur trioxide. A temperature of -35-55 C., or as high as 75 C., if need be, is particularly suitable" and themass maybe stirred for approximately 340 hours, until tests indicate that both the sulfonationreaction and the condensation'rea'ction are complete. with water until it shows a tendency to separate readily. It is. then permittedtc remain in a quiescent state, until such separation i s' complete. The lower layer of dilute acid is withdrawn and the .acidic 'mass is neutralized so t/hat maybe employed. such basic materials include The sulfonated-massis then diluted Example 5 A bis-P1181161; obtained from ,phenol and dibenzyl-ketone, is employed in place of bis-phenol a. in Example; 1, preceding.

A bis-phenol, derived from cyclohexanone and phenol, iissused to replace bis-phenol A in Exam- 11, preceding.

' Example 7 :1 pound'pmole .oildi-phenyl dimethyl methane this-phenol A), .is .mixed with 1 pound. mole of propyl. hydrogen sulfate. and 1 pound mole of :oleic hydrogenehydrogen sulfate, 2 to 3 poundmolesi ofnsulfuric acid-9.6% or weak oleum are: added; The mass is stirred constantly at a. temperature varying from 35 to -C., or as asz'fl5 ifneed :be, for approximately 3-10 hours; until tests indicate that :both suli'onation reaction fl ndcondensation reaction are complete. sulflmated. mass .isthen diluted with water. until it; shows. a. tendency to separate readily. It is then permitted to remain in a quiescent state such separation: is .complete. The lower mer-oiadi'luteacid. is withdrawn and the acidic mass neutralizedhwith a base whichenhances, or, iatleast does not markedly reduce water solubilitae. qsuch'ibasic materialsv include caustic soda,

ammonium hydrate, triethanolamine, .oxyethylated.=triethanolamine, oxyethylated :triethanolaminederiveddby treating triethanolaminewwith ethylene oxide, oxyethylated t'rismydroxymethyl) aminomethane, derived by .trcatingttris hydroxymethyl) aminomethane with efihyienemddqetc.

Example 8.

The same'procedure is followed as in Example 7, preceding, except that 2-4 moles of propyl hydrogenisuliateare employed for each mole of the-ar-ylrelwtant;

Example 9 The same procedure is followed as in Example- 7, preceding, except that butyl hydrogen sulfate, amyl hydrogen sulfate, hexyl hydrogen sulfate, or octyl hydrogen sulfate, is substituted in place of propyl hydrogen sulfate.

Example 10 The same procedure is followed as in Example '7, preceding, except that a mixture of at least two different .alkyl hydrogen sulfates are employed in each instance. For example, a mixture of propyl hydrogen sulfate and butyl hydrogen sulfate, or butyl hydrogen sulfate and amyl hydrogen sulfate, or propyl hydrogen sulfate and amyl hydrogen sulfate, are used.

' Example '11 In the previous examples where a cumyl phenol or a bis-phenol is subjected tocondensation with an alkyl hydrogen'sulfate, in thejpresence of sulfuric acid, there is employed instead a conven-' tional Friedel & Crafts reaction, involving one mole of the selected aryl reactant and 1 to 4 moles of an alkyl halide, for instance, propyl chloride, butyl chloride, amyl chloride, hexyl chloride, octyl chloride, and decyl chloride, in

the presence of aluminum chloride, so as to cause Example 12 The same procedure is followed as in Examples 1-11, preceding, except that erucic acid is employed instead of oleic acid.

Example 13 The same procedure is followed asin Examples 1-11, preceding, except that the mixed fatty acids derived from sunflowerseed oil or teaseed oil, are

used insteadpf oleic acid.

Example 14 The same procedure is followed as in Examples 1-13, preceding, except that the acidic mass is employed, as such, or after neutralization with a base which tends to reduce water solubility, and

in fact, may result in a compound which is either oil-soluble, or almost water-insoluble, or completely water-insoluble, or may show extreme water-solubility in either water oroil. Among the suitable bases for such purposes are: pyridine, cyclohexylamine, dicyclohexylamine, benzylamine, di-benzylamine, amylamine, di-amylamine, tri-amylamine, octadecylamine, and particularly high molal amines, which, in the form tate, show surface activity.

Errample 15 The same procedure is followed as in Exam ples 1 to 13, preceding, except that thefinal product, as far as the sulfonic radical is concerned, is converted into the salt of a quaternary ammonium base. The particular ammonium bases employed are characterized by the type in which salts having a low molal anion are surface-active,

of the acei. e., quaternary bases of the kind that the chloride, nitrite, bromide, acetate, lactate, and the like, show surface-activity in aqueous solution. Generally speaking, such quaternary compounds are more apt to be available in the form of salts, for instance, a chloride or bromide, rather than in the form of the free base. In light of this fact,

salts of the kind herein contemplated, i. e., sulfonates, are bestfobtained metathetically, The

two conventional procedures for such metathetical reactions involve preparing the sodium, potassium, the ammonium salt of the sulfonic acids previously described, and then reacting an alcoholic solution of such salts with an alcohol solution of the quaternary chloride or bromide. Another procedure involves the-principle that the combination 'of a surface-active anion and surface-active cation is apt, to 'produce a salt which is insoluble in'water, in the absence of an excess of either reactant." Thus, anaqueous solution .of the sodium, potassium, or ammonium salt of the kind described in the preceding examples maybe reacted in dilute solution, for instance, 5% with a 5% solution of cetyl pyridinium bromide, or any one of a number of other surface-active quaternary halides, as, for example, those described in our co-pending application Serial No. 463,439, filed October 26, 1942.

Efim ze 16 The same procedure is followed as in Examples 1-15, preceding, except that the carboxyl radical is converted into a hydrophile group by neutralization with caustic soda, caustic potash, am-

monium hydroxida or any one of a number of. hydroxylated amines or the like which enhance water solubility. I

Ewample ii' The same procedure is followed as in Example 16, preceding, except that the amine used to react with the carboxyl radical is one of the kind gig which e reases water-solubility, such as amylamine, cyclohexylamine, benzylamine, etc.

Example 18 The same procedure is followed as in the preceding examples, insofar as the production of the acidic mass, containing the sulfo-aromatic resultant is concerned, but prior to any washing or diluting step. At this point the acidic mass, prior to dilution, ismixed witha low molal alcohol, such as ethyl alcohol, propyl alcohol, butyl alcohol, or the like, in such amounts that there is present at least 2 moles of the selected alcohol for each carboxyl radical. The acidic mass is a stirred until uniform, and then sulfuric acid, 96%

strength, is added in amounts equivalent to 3 moles of sulfuric acid for each mole of alcohol added. The alcohols added are anhydrous, or preferably, substantially anhydrous. The acidic mass so obtained is'permitted to stand for approximately 3-10 days at approximately 20-35 C., until the esterification reaction is substantially complete, as indicated by substantial disappearance of free carboxyl radicals. The acidic mass is then separated in the conventional manner previously described, and the sulfonic acid radical and any residual 'carboxyl radical present are neutralized by means of any one of the.

basespreviously indicated, which may be of the type that enhance water solubility, or decrease water solubility. The excess of low molal alco- 1101 present is'permitted to remain orbe removed by distillation. I Attention is directed .to another variation; sub-genus which is particularlyvaluable. Such sub-genus or sub-division is obtained by-oxyethylation of the aryl compound. Oxyethylation is conducted bymeansof compounds-having a reactive ethylene .oxide ring, suchas, for example, ethylene oxide, propylene oxide, butylene oxide, etc. .If such oxyethylation isconducted prior to a Friedel- & Craftsmeaotion; it is obvious that the alkyl-group introduced isi-attached .to the nuclear carbon atom by-an. oxyethylene radical or a .polyoxyethylene.radical. 'Similarly,'the

hydroxyl group, after oxyethy-lation, represents a similar situation in which: the hydrogen :bond is interrupted byian oxyalkylene radicaL-on a .polyoxyalkyleneradical. :Inanywevent, thenumber of oxyalkylene radicals introduced' is limited-so that water solubility isinot obtained in:the absence of a sulfonic group. Generally speaking, this means that the polyoxyalkylene radical appearing between a nuclear carbonatom and a hydrogen atom, or betweena nuclear carbon atom andzanalkyl radical, will contain not over ether linkages. This relationship is indicated in the .following manner, the arrow: indicating oxyalkylation, and more ,particularly, xoxyethylation.

in which. R1 is a member of-the. classselected from alkyl, alicyclic and alkylaryl -radica-ls; Rais a member selected from the class consisting of alkyl, alicyclic and alkylaryl radicals and hydrogen atoms; R3 is an alkyl radical containing not over 10 carbon atoms; R4 is-an alkyl radical containing not over 2 carbon atoms;

is the fattyacid residue of the unsaturated fatty acid Rc RsCOOH, and R7 is a member of the class of aliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals, arylalkyl hydrocarbon radicals and cations, including hydrogen; M is a cation. includinghydrogen; X. is a member of the class consisting of oxygen atoms; oxyalkylene radicalsin-which the-alkylene radical does not containmore than 4 carbon atoms, and polyoxyalkylene radicals in which the alkylene radical does not" contain more than 4 carbon atoms and the'ether linkage'dces'not appear more than 10 times; and y is a small Whole number including zero; yflis a zero or one, with the proviso that there must be at leastone occurrence of at least one occurrence of X and at least one occurrence OfSOsM.

In examining the previous formula, it is apparent that the trivalent radical is the fatty acid residue ofthe unsaturated fatty acid I Re=R5COOH In the reaction of the kind noted, the double bond of the fatty acid radical becomes saturated by the introduction of the aromatic nucleus, and the nuclear hydrogen atom. Actually, it is immaterial whether the nuclear hydrogen atom attaches itself toradical R5 and the aryl radical to R6, or inversely, the hydrogen atom to R6 and the aryl radical to R5. One form is simply the metamer of the other-form. Any isomeric or metameric form is equally satisfactory. It is understood that the formulas in the hereto appended claims include all isomeric, and particularly, all metameric forms. Any ordinary oleic acid ethylene linkage, appears at the 9-l0 carbon atom position. With other unsaturated acids the position might vary. The formula brings out clearly the fact that the'fatty acid radical is nuclearly linked so as' to present a branch chain arrangement.

Chemical products or compounds of the kind above described, are adapted to be used as demulsifiers in the'resolution of petroleum emulsions'of thewater-in-oil type; they are adapted to be used in the removal of a residual mud sheath which remains after drilling a wellby the rotary method; they may be used as a break inducer in doctor treatment of the kind intended to sweeten gasoline; certain of said products are of value as surface tension depressants in the acidification of calcareous oil-bearing strata by means of a strong mineral acid, such as hydrochloric acid; and some of said products are capable of use as wetting agents in thefiooding of exhausted'oil-bearing'strata, and for'various other uses where wetting agents of the conventional type are employed. As to some of such uses' which are well known, see The expanding application of wetting agents, Chemical Industries, volume 48, page. 324 (1941) Having thus described our invention, what we claim as new and desire to secure'by Letters Patent is:

1. A new chemical product, comprising, a'diaryl substituted methane sulfonate, in which the aryl radicals are monocyclic and-the sulfonic acid radical is nuclearly linked; and of the'formula:

in which R1 is a member selected fromthe consisting of alkyljalicyclicand alkylaryl raidicals; R2 is a member selected from-the class consisting of alkyl, alicyclicand alkylaryl radicals and hydrogen atoms; R3 is an alkyl radical containing not over 10 carbon atoms; R4 is an alkyl radical containing-not over 2 carbon atoms is the fatty acid residueof the unsaturatedhigher fatty acid, I '1 4 Rs -Rs-COQH and'Rq is a'member selcted-irom' the class con-- sisting of aliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals, arylalkyl hydroc bon radicals, andcations, including hydrog M is a'cation includingihydrogen; X is a me ber of the class consisting of oxygen atoms, oil-3Y alkylene radicals in whichthe alkyleneradica'l does not contain more than 4 carbon atoms, and polyo'xyalkylene radicals in" which the alkylene radical does not contain" "more than 4 carbon atoms and the ether linkage doesnot appear mo than times; and y is a small whole num 1r including zero; 11 is a zero or one, with the pro viso that there must be at least one occurreiflilcc of the monovalent radical, HIt-f-RsCOOB-w, at least one occurrence of X and at least one old currence of SOsM. I

2. A new chemical product, comprising-a diaryl r substituted monosulfonate; in which" the ajr' yl radicals are monocyclic and the sulfonic radical is nuclearly linked, and of the formula:

. o V (R4),. H.115

(SO:M),

substituted methane sulfonate, in, which the aryl sisting of alkyl, alicyclic and alkylaryl radicals and hydrogen atoms; R3 is an alkyl radical containing not over 10 carbon atoms; R4 is an alkyl radical containing'not over 2 carbon atoms;

' cyclic hydrocarbon radicals, arylalkyl hydrocar bon radicals, and cations, including hydrogen; M is a cation including hydrogen; X is a member of the class consisting of oxygen atoms, oxyalkylene radicals in which the alkylene radical does not contain more than 4 carbon atoms, and polyoxyalkylene radicals in which the alkylene radical does not contain more than 4 carbon atoms and the ether linkage does not appear more than 10 times; and y is a small Whole number including zero; y is a zero or one, with the-proviso that there must be at least one occurrence of R3, at least one occurrence ofthe monovalent radical and at least one occurrence of $03M.

3. A new chemical product, comprising a diaryl radicals are .monocyclic andthe sulfonic acid radical is nuclearl linked, and of the formula:

' whichRrand R2 are methylradicals; is an alkyl radical containing not over 10 carbon atoms; R4 is an alkyl radical containing not over 2 carbon atoms; H

. -Rl|l Et .C o 0- is the, fatty acid residue of the unsaturated higher a y'a i f Rs=R5-COOH and R7 is a member selected from the class consisting of aliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals, arylalkyl hydrocarbon radicals, and cations, including hydrogen; M is a cation including hydrogen; X is a member of the class consisting of oxygen atoms; oxyalkylene radicals in which the alkylene radical does not contain more than 4 carbon atoms, and polyoxyalkylene radicals in which the alkylene radical does not contain more than 4 carbon atoms and the ether linkage does not appear more than 10 times; and y is a small whole number including zero; 1y is ;-aazero phone, with 1-, the proviso;that there lmustwbe at least one occurrence of "the monovalent radical l I min-raccoon,

- 30 in which R1 and -Rz are ethyl-radica1s; R3 is an alkyl radical containing not over 10 carbon atoms;R4 is an -alkyl radical containing not over 2 carbon-atoms;

is the fatty acid residue of the unsaturated higher fatty acid v .R, =R5--CO0H and R7 is a member selected from the class consisting of aliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals, arylalkyl hydrocarbon radicals, and cations, including hydrogen; M is a cation including hydrogen; X is a member of the class consisting of oxygen atoms, oxyalkylene, radicals in which the alkylene radical does not contain more than 4 carbon atoms, and polyoxyalkylene radicals in which the-alkylene radical does not contain more than 4 carbon atoms and the etherlinkage does not appear more than 10 times; and y is a-small whole number including zero; y is a zero or one, with the proviso that there'must-be at least one occurrence out the monovalent radical at least one occurrence of Xand at least one occurrenceof $03M.

5. A new chemical product, comprising adiaryl substituted methanesulfonate, in which the aryl radicalsmare; monocyclic 1 and :the sulfonic acid radicalsda 'nuclearl-yz linkednandnof the formula:

I: I. v. Eliza] inlwhich" R1 isamethyl radicaland'Rz is an ethyl radical; is an :,a1kyl yradical containing not over 10 -carbonatoms,'"R4 is: an alkyl radical containing'not cver'2 carbomatoms;

Rs1 1a-:-Q 0- is the fatty acid residueof' the unsaturated higher fatty acid Ra==R5--=OOH and'R is a member selected from the class consisting of aliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals,--arylalkylhydrocarbon radicals, rand cations, -including-l hydrogen; M is a cation including hydrogen; X is -a member of the class consisting'oi oxysen atoms, oxyalkylene radicals in whichthe alkylene radical does not Q in m re than 4- Carbon-atoms, and polyoxyall zyleneradicals in which the-.alkyleneradical does.- not contain more than 4 carbon atoms and the ether linka e vdoes not ,appearmore than 10 times; and y is'Ia, small whole numbercincluding zero; -y is ,a, zero or.one,.with the proviso that there, .must a. be ,at .least one ioccurrence of the monovalent radical y I I H.Rul ll-(lo QR1. at: least one occurrence of rX sand-at least one occurrence ,ofa'sQsM.v

6. In the manufacture of thechemical product described-in clain'rl, thevsteps-o f: (a); subjecting a ms-phenol to a condensation.sulfonation reaction in ,therpresence of .-,.an unsaturated higher fattyl-iaci'd and :an r,excess "of sulfuric acid; (b)- diluting the acidic reaction mass with water until there is an incipient tendency to settle; and (c) permitting the diluted reaction mass to stand in a quiescent state until separation is complete 60 with a subsequent-withdrawal of the dilute acid.

MELVIN DE GROOTE. BERNHARD KEISER. 

